US9200216B2 - Process for oligomerizing olefins - Google Patents
Process for oligomerizing olefins Download PDFInfo
- Publication number
- US9200216B2 US9200216B2 US13/394,827 US201013394827A US9200216B2 US 9200216 B2 US9200216 B2 US 9200216B2 US 201013394827 A US201013394827 A US 201013394827A US 9200216 B2 US9200216 B2 US 9200216B2
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- United States
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- group
- alkyl
- support material
- ionic liquid
- substituted
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- 238000000034 method Methods 0.000 title claims description 54
- 150000001336 alkenes Chemical class 0.000 title claims description 35
- 230000003606 oligomerizing effect Effects 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000002608 ionic liquid Substances 0.000 claims abstract description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 239000012190 activator Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 4
- 230000002152 alkylating effect Effects 0.000 claims abstract description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 4
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 4
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 40
- -1 mixed oxides thereof Chemical compound 0.000 claims description 31
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 150000005840 aryl radicals Chemical class 0.000 claims description 6
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 150000001399 aluminium compounds Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 238000006384 oligomerization reaction Methods 0.000 abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000012071 phase Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical class CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 0 [1*]N1CCN([3*])C1[2*].[4*][CH2+] Chemical compound [1*]N1CCN([3*])C1[2*].[4*][CH2+] 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 6
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical class CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000007172 homogeneous catalysis Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- UPSVYNDQEVZTMB-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene;1,3,5,7-tetranitro-1,3,5,7-tetrazocane Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O.[O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UPSVYNDQEVZTMB-UHFFFAOYSA-N 0.000 description 2
- 229910017048 AsF6 Inorganic materials 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000004639 Schlenk technique Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical class CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- GMQVFHZSXKJCIV-UHFFFAOYSA-N 2,2,2-trifluoro-n-(2,2,2-trifluoroacetyl)acetamide Chemical compound FC(F)(F)C(=O)NC(=O)C(F)(F)F GMQVFHZSXKJCIV-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical class CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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Definitions
- the present invention relates to a multi-component catalyst system and to its use in a process for oligomerizing C 3 to C 5 olefins from olefin-containing hydrocarbon mixtures.
- the low molecular mass oligomers of olefins are intermediates which are used, for example, for preparing aldehydes, carboxylic acids and alcohols.
- the C 8 olefins formed by oligomerization from linear butenes can be reacted by hydroformylation and subsequent hydrogenation to give the corresponding nonanols, which in turn are used primarily for preparing plasticizers.
- Starting materials which can be used for the preparation of the oligomers include pure olefins with a double bond in a position, pure olefins with an internal double bond, and mixtures of these olefins.
- Particularly economic processes for preparing the oligomers are those using mixtures of ⁇ -olefin and olefins with an internal double bond, and optionally paraffins.
- the degree of branching is frequently a criterion.
- One measure of the degree of branching is the iso index. It is defined by the number of branches per molecule. For example, linear octenes (n-octenes) have an iso index of 0, methyl heptenes an iso index of 1, and dimethyl hexenes an iso index of 2.
- the calculation of the iso index of mixtures takes account of the mass fractions of the individual groups of compounds. The lower the iso index of a mixture, the more linear, on average, the compounds present therein.
- the iso index of an olefin mixture defines the lowest possible degree of branching of the derivative products, and hence is a co-determinant of their profile of performance properties.
- oligomerization of olefins is carried out industrially either in homogeneous phase, over a molecular catalyst, or heterogeneously, over a solid catalyst.
- a regime with homogeneus catalysis is described, for example, by A. Chauvel and G. Lefebvre in Petrochemical Processes, volume 1, Editions Technip 1989, pp. 183-187.
- One process with homogeneous catalysis that is practised worldwide is the oligomerization with soluble molecular nickel complexes, known as the DIMERSOL process (see Yves Chauvin, Helene Olivier, in “Applied Homogeneous Catalysis with Organometallic Compounds”, edited by Boy Cornils, Wolfgang A. Herrmann, Verlag Chemie, 1996, pp. 258-268).
- nickel compounds For the non-acidic, heterogeneously catalysed oligomerization of olefins, it is common in industry to use nickel compounds on support materials.
- One catalyst of this kind is a nickel fixed bed catalyst which is employed in the Applicant's OCTOL process (Hydrocarbon Process., Int. Ed. 1986, Vol. 65, pp. 31-33).
- the non-acidic, heterogeneously catalysed oligomerization of olefins leads, under optimized conditions, to products having a higher linearity than with the acidic heterogeneous catalysts. Nevertheless, there are limits to the linearity of the products.
- the iso index is greater than 1, and the level of production of the unwanted dimethylhexenes is around 15% to 30%.
- Homogeneous molecular catalysts as a result of possibilities for varying the ligands, and as a result of their more highly defined structure, possess a greater potential for optimizations, and hence lead frequently to oligomerization catalysts whose selectivity for linear products is higher, and with which dimethylhexenes are produced as reaction products to a lesser degree.
- a disadvantage which occurs both with homogeneous and with heterogeneous catalysts is the sharply falling selectivity for dimeric reaction products at high conversions. With increasing conversions there is a sharp increase in particular in the fraction of trimeric, tetrameric and higher oligomers. This results in increased cost and complexity for product separation, and in losses in yields, or else, if the higher oligomers can be used alternatively, which is economic only in the case of large oligomerization plants, leads to a higher cost and complexity for logistics and storage. With relatively small reactant streams in particular, therefore, it is advantageous if trimers, tetramers and higher oligomers are produced in the reaction not at all or only to a small extent.
- a particularly high selectivity for dimeric oligomerization products is frequently achieved through the use of a 2-phase reaction regime.
- the catalyst is located in a polar phase, while the products are located in—or themselves form—an apolar phase. Accordingly, in the catalyst phase, the dimers that are desired as reaction products are available only to a small extent for consecutive reactions to higher oligomers.
- One example of the application of a 2-phase reaction regime with an ionic liquid as polar catalyst phase is the DIFASOL process (Gilbert et al., Oil & Gas Science and Technology—Rev. IFP 2007, Vol. 62, pp. 745-759).
- the object therefore, was to combine the advantages of a heterogeneously catalysed reaction, such as uncomplicated processing of the reaction mixture and ease of product separation, for example, with the advantages of a homogeneously catalysed reaction, such as high conversions and a simpler capacity for optimization leading to higher selectivities, for example.
- SILP catalysts for short—can be utilized in the oligomerization of C 3 to C 5 olefins.
- SILP catalysts are catalysts in piece form which are composed of a solid support material enveloped with an ionic liquid in which the active catalytic composition is present in solution.
- the principle of the immobilization of a molecular catalyst in a film of an ionic liquid on a solid support was first described in WO 2002098560.
- the present invention provides a catalyst system composed of:
- the present invention further provides a process for oligomerizing olefins having 3 to 5 carbon atoms using the catalysts of the invention.
- the invention provides more particularly a process for preparing a mixture of C 8 olefins from a mixture of 1-butene, cis- and trans-2-butene and the unreactive component n-butane.
- Suitable support materials for the catalysts of the invention include carbon nanotubes, activated carbon, magnesium oxide, aluminium oxide, zirconium oxide and silicon dioxide and also their mixed oxides.
- the support materials may contain up to 1.5% by mass of alkali metal oxides.
- hydroxyl groups on the surface of the support materials may be dehydroxylated and/or protected with organosilicon radicals.
- silicon dioxide and activated carbon are preferred as support materials. Particular preference is given to using silicon dioxide having a particle size of between 0.05 mm and 4 mm and a BET surface area of 250 to 1000 m 2 /g, as determined in accordance with DIN 66131 and 66132, and also activated carbon having a BET surface area of between 1000 and 4000 m 2 /g. It is especially preferred to use silica gel having a particle size of between 0.063 mm and 0.2 mm and a BET surface area of between 300 and 800 m 2 /g.
- ionic liquid for the catalysts of the invention compounds are used in which the anion is selected from the group consisting of tetrafluoroborate ([BF 4 ] ⁇ ), hexafluorophosphate ([PF 6 ] ⁇ ), dicyanamide ([N(CN) 2 ] ⁇ ), bistrifluoromethylsulphonylamide ([NTf 2 ] ⁇ ), tricyanomethide ([C(CN) 3 ] ⁇ ), tetracyanoborate ([B(CN) 4 ] ⁇ ), halides (Cl ⁇ , Br ⁇ , F ⁇ , I ⁇ ), hexafluoroantimony ([SbF 6 ] ⁇ ), hexafluoroarsenate ([AsF 6 ] ⁇ ), sulphate ([SO 4 ] 2 ⁇ ), tosylate ([C 7 H 7 SO 3 ] ⁇ ), nonaflate ([C 4 F 8 SO
- the cation is selected from:
- imidazole nucleus may be substituted by at least one group selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 substituted aminoalkyl, C 5 -C 12 substituted aryl or C 5 -C 12 substituted aryl-C 1 -C 6 alkyl groups, pyridinium cations of the general formula
- pyridine nucleus may be substituted by at least one group selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 substituted aminoalkyl, C 5 -C 12 substituted aryl or C 5 -C 12 substituted aryl-C 1 -C 6 alkyl groups, pyrazolium cations of the general formula
- pyrazole nucleus may be substituted by at least one group selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 substituted aminoalkyl, C 5 -C 12 substituted aryl or C 5 -C 12 substituted aryl-C 1 -C 6 alkyl groups; and triazolium cations of the general formula
- the triazole nucleus may be substituted by at least one group selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 substituted aminoalkyl, C 5 -C 12 substituted aryl or C 5 -C 12 substituted aryl-C 1 -C 6 alkyl groups, and the radicals R 1 , R 2 , R 3 are selected independently of one another from the group consisting of the following:
- halides Cl ⁇ , Br ⁇ , F ⁇ , I ⁇
- the process of the invention preferably uses ionic liquids having the following cations:
- imidazole nucleus may be substituted by at least one group selected from C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 substituted aminoalkyl, C 5 -C 12 substituted aryl or C 5 -C 12 substituted aryl-C 1 -C 6 alkyl groups.
- the catalytically active composition composed of a nickel complex, its precursor(s) and optionally an activator.
- the catalytically active composition is generated from one or more precursors and optionally an activator, under process conditions, or is supplied to the process already in the form of an active catalyst.
- NiX 2 (with X ⁇ Cl, Br), Ni(acetylacetonato) 2 , Ni(hexafluoroacetylacetonato) 2 , Ni(cyclooctadienyl) 2 , Ni(cyclopentadienyl) 2 , Ni 2 ( ⁇ 3 -allyl)( ⁇ -Cl 2 ), Ni 2 ( ⁇ 3 -allyl)( ⁇ -Br 2 ), Ni 2 ( ⁇ 3 -methallyl)( ⁇ -Cl 2 ), Ni 2 ( ⁇ 3 -methallyl)( ⁇ -Br 2 ), Ni( ⁇ 3 -allyl) 2 , Ni( ⁇ 3 -methallyl) 2 , NiX 2 (PR 1 R 2 R 3 ) 2 (with X ⁇ Cl, Br and R 1 ,
- 1,3-diketones Preference is given to using 1,1,1,5,5,5-hexafluoroacetylacetone, 2,2,2-trifluoro-N-(2,2,2-trifluoroacetyl)acetamide and acetylacetone.
- the realizable mass ratio of ionic liquid to support material is dependent on physical properties. Particularly critical for the ionic liquid is the density, and for the support material the pore volume. More specifically, the pore radius distribution of the support, and the wetting characteristics of the ionic liquid on the surface of the support, have an influence.
- the ionic liquid may be applied in a wide mass ratio relative to the support.
- the preferably used ionic liquid (1-butyl-3-methylimidazolium chloride/aluminium chloride)
- mass ratios of 0.034 to 0.334 are particularly preferred.
- mass ratios of 0.022 to 2.171 are particularly preferred.
- mass ratios of 0.217 to 0.543 are particularly preferred.
- mass ratios of ionic liquid to support material of 0.012 to 1.255 are used with preference.
- Particularly preferred are ratios of 0.063 to 0.628.
- the realizable mass ratios of nickel to ionic liquid are generally dependent on the nature of ionic liquid and on the nature of the support material.
- the particularly preferred mass ratios of ionic liquid to support material are from 0.126 to 0.314. Mass ratios of nickel to ionic liquid of 0.003 to 0.027 are used. Preferred are ratios of 0.010 to 0.020. Particularly preferred is the ratio from 0.010 to 0.011.
- the catalysts of the invention can be prepared by treating the solid support material with a homogeneous solution comprising the other catalyst components and optionally a solvent.
- One way is to impregnate the solid support material with a solution of this kind. In that case an excess of solution is added to the support material. Following mass transfer between support material and solution, which may be accelerated by shaking or stirring, the excess liquid is removed mechanically from the catalyst in piece form, by filtration or centrifuging, for example. This may be followed by a drying step.
- Another method is to spray the support material with a solution of this kind. If desired, any added solvent is removed during or after the spraying operation.
- the catalyst is prepared preferably by adding to the support material a solution which is composed of the other catalyst components and a solvent, and evaporating the solvent.
- Solvents used for this purpose are preferably low-boiling compounds which form a homogeneous solution with the other catalyst components and which do not react with any of these components. Examples of suitable solvents include dichloromethane, hexane and toluene. One especially preferred solvent is dichloromethane.
- the solvent is separated off in the pressure range from 10 5 to 2*10 2 Pa, with the pressure being lowered successively, starting from atmospheric pressure.
- the preparation procedure takes place in the absence of oxygen and of water.
- the supported catalysts of the invention are prepared preferably in a form which offers a low flow resistance during the oligomerization. Typical forms are tablets, cylinders, strand extrudates or rings.
- the shaping in this case takes place generally on the support material prior to application of the ionic liquid and of the catalyst components in solution therein. It is also possible to use granular supports for preparing the catalysts of the invention. By extractive sieving it is possible in that case to separate out a catalyst support having the desired particle size. Support materials can frequently be obtained commercially as shaped bodies.
- the feed stocks may be composed of olefins with the same, similar ( ⁇ 2) or markedly different (>2) C number.
- 2-butenes and 1-butene Used more particularly are mixtures of 2-butenes, 1-butene, and linear and branched butanes, of the kind produced in the work-up of the C 4 cut from a steamcracker after the removal of the polyunsaturated compounds and of the isobutene.
- FIG. 1 A flow diagram of the stirred tank reactor used for the batch dimerization is shown in FIG. 1 .
- the Hastelloy autoclave possesses a motor-driven stirring unit (gas introduction stirrer, Heidolph RZR 2020 motor) and also a pressure indicator (PI) and temperature indicator (TI 1).
- the overpressure valve V-5 which opens at 80 bar, prevents an excessive, unwanted increase in pressure within the reactor. Via the valves V-1, V-2 and V-3 it is possible to pass reactants and also inert gas into the stirred tank. Samples can be taken during a catalyst experiment via valve V-4.
- the procedure adopted was as follows: using the Schlenk technique, the SILP powder prepared was inserted into the reactor under inert gas conditions, and the reactor was screwed shut. Through an opening in the lid, 80 ml of cyclohexane (water content ⁇ 20 ppm) were introduced. Approximately 1 ml of n-nonane as internal GC standard and 6 ml of ethylaluminium dichloride (0.1 molar solution in hexane, available commercially) were added, and the opening in the lid was closed.
- the preparation of the catalytically active composition and the implementation of the experiments were in accordance with the procedures described above.
- the reactant employed was a mixture of 70% n-butane, 19% trans-2-butene, 9% cis-2-butene, 1.7% 1-butene and 0.3% isobutane+C 5 alkanes.
- the reactant mass is based on the mixture.
- the conversion is based only on the butenes present.
- Entry 1 from Table 1 shows that, with the inventive catalyst system using NiCl 2 (PPh 3 ) 2 , ethylaluminium dichloride as activator, a mixture of 1-butyl-3-methylimidazolium chloride and aluminium chloride in a ratio of 1/1.1 as ionic liquid, and silica gel as support material, it is possible to obtain a C4 hydrocarbon having a low olefin content of approximately 30%, a very high selectivity of 94% for the desired dimeric reaction products and at the same time a low selectivity (11.6%) for the unwanted dimethylhexene.
- the iso index is 1.
- Entry 2 from Table 1 shows the use of 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate as an ionic liquid under otherwise identical conditions.
- C 8 oligomers even higher selectivities for the C 8 oligomers are obtained, but the conversion is lower.
- the selectivity for dimethylhexenes is very low, at about 10%.
- a very good iso index of ⁇ 1 is obtained.
- Entry 3 from Table 1 shows the use of activated carbon as support material.
- the selectivity for dimethylhexenes is particularly low, and a particularly low iso index, for a conversion of 40%, is achieved.
- Entry 4 from Table 1 shows the use of silica gel which has been dehydroxylated by silylation.
- a very good iso index of ⁇ 1 is achieved.
- the particular feature of this example is that very little ionic liquid is needed, as illustrated by what is by far the lowest IL/support material ratio, with a value of 0.067.
- the purely homogeneously catalysed Dimersol process referred to at the outset produces up to 40% of dimethylhexenes.
- the iso index is typically 1 to 1.35, and the selectivity for C 8 oligomers in that process is ⁇ 90%.
- the catalyst systems of the invention are superior to the Dimersol process in respect both of selectivity for C 8 oligomers and of linearity of the products, and particularly with respect to a low dimethylhexene selectivity.
- the reaction regime with the catalyst systems of the invention is considerably simpler, since on account of their immobilized character they can be separated easily from the products.
- the selectivity for dimethylhexenes is around 15% to 30%, with an iso index which is typically >1.
- the dimer selectivity is ⁇ 90% (see Albers et al., Oligomerisation of C 3 -C 5 on Solid State Nickel Compounds: Complex Catalysts for a versatile Reaction, DGMK-Tagungsbericht 2004-3).
- the catalyst systems of the invention are superior to this process in respect both of the selectivity for C 8 oligomers and of the linearity of the products, particularly with respect to a low dimethylhexene selectivity.
Abstract
- a) a support material selected from at least one of the following materials: silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide and mixed oxides thereof, carbon nanotubes;
- b) an ionic liquid;
- c) a catalytically active composition comprising nickel;
- d) an activator selected from the group of Lewis acids with alkylating properties.
Description
- a) a support material selected from at least one of the following materials: silicon dioxide, aluminium oxide, magnesium oxide, zirconium oxide and mixed oxides thereof, carbon nanotubes;
- b) an ionic liquid;
- c) a catalytically active composition comprising nickel;
- d) an activator selected from the group of Lewis acids with alkylating properties.
- a) As catalysts in piece form, SILP catalysts have the typical advantages of heterogeneous catalysts as described in Jens Hagen, Industrial Catalysis: A Practical Approach, 2006, 2nd Ed., Wiley-VCH, p. 12.
- b) In contrast to 2-phase systems, there is no need for phase separation between reaction component and work-up component and also solvents.
- c) Since the actual catalyst is a molecular complex, the SILP catalysts have the typical advantages of homogeneous catalysts as described in Jens Hagen, Industrial Catalysis: A Practical Approach, 2006, 2nd Ed., Wiley-VCH, p. 12.
- d) A further particular advantage with the process of the invention is the high linearity of the products and particularly the low level of formation of dimethylhexenes.
- e) Since the catalytically active component is present in a polar phase, the selectivity for dimeric reaction products is very high. The polar phase is only a thin film, however, and so mass transport usually has no limiting effect.
-
- quaternary ammonium cations of the general formula [NR1R2R3R4]+,
- phosphonium cations of the general formula [PR1R2R3R4]+,
- imidazolium cations of the general formula
where the imidazole nucleus may be substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 substituted aminoalkyl, C5-C12 substituted aryl or C5-C12 substituted aryl-C1-C6 alkyl groups,
pyridinium cations of the general formula
where the pyridine nucleus may be substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 substituted aminoalkyl, C5-C12 substituted aryl or C5-C12 substituted aryl-C1-C6 alkyl groups,
pyrazolium cations of the general formula
where the pyrazole nucleus may be substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 substituted aminoalkyl, C5-C12 substituted aryl or C5-C12 substituted aryl-C1-C6 alkyl groups; and triazolium cations of the general formula
where the triazole nucleus may be substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 substituted aminoalkyl, C5-C12 substituted aryl or C5-C12 substituted aryl-C1-C6 alkyl groups,
and the radicals R1, R2, R3 are selected independently of one another from the group consisting of the following:
-
- hydrogen;
- linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups having 1 to 20 carbon atoms;
- heteroaryl, heteroaryl-C1-C6 alkyl groups having 3 to 8 carbon atoms in the heteroaryl radical and at least one heteroatom selected from N, O and S, which may be substituted by at least one group selected from C1-C6 alkyl groups and/or halogen atoms;
- aryl, aryl-C1-C6 alkyl groups having 5 to 12 carbon atoms in the aryl radical, which optionally may be substituted by one or more C1-C6 alkyl groups and/or halogen atoms;
- and the radical R4 is selected from:
- linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups having 1 to 20 carbon atoms;
- heteroaryl-C1-C6 alkyl groups having 4 to 8 carbon atoms in the aryl radical and at least one heteroatom selected from N, O and S, which may be substituted by one or more C1-C6 alkyl groups and/or halogen atoms;
- aryl-C1-C6 alkyl groups having 5 to 12 carbon atoms in the aryl radical, which optionally may be substituted by one or more C1-C6 alkyl groups and/or halogen atoms.
where the imidazole nucleus may be substituted by at least one group selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 substituted aminoalkyl, C5-C12 substituted aryl or C5-C12 substituted aryl-C1-C6 alkyl groups.
TABLE 1 |
Example experimental results with the inventive catalyst system: catalyst |
precursor NiCl2(PPh3)2; temperature: 20° C.; activator: 6 ml EtAlCl2 solution |
(0.1 molar solution in hexane) |
IL/support | Conversion | Iso | |||||||
Support | material | 60 min | SC8 | index | SDMH | SMH | SOct | ||
No. | Ionic liquid | material | [—] | [%] | [%] | [—] | [%] | [%] | [%] |
1 | [BMIM]Cl/AlCl3 | Silica | 0.126 | 69.4 | 94.2 | 1.0 | 11.6 | 76.8 | 11.6 |
2 | [EMIM][FAP] | Silica | 0.171 | 12.6 | 98.8 | 0.97 | 9.9 | 77.1 | 13.0 |
3 | [BMIM]Cl/AlCl3 | Activated | 0.217 | 40.3 | 94.2 | 0.96 | 7.6 | 81.0 | 11.4 |
carbon | |||||||||
4 | [BMIM]Cl/AlCl3 | Si silica | 0.067 | 33.7 | 97.8 | 0.97 | 9.8 | 77.2 | 13.0 |
[BMIM]Cl/AlCl3 = 1-butyl-3-methylimidazolium chloride/aluminium chloride ( |
|||||||||
[EMIM][FAP] = 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)tri-fluorophosphate, silica gel: Merck KGaA type 10184 (particle size 0.063-0.200 mm, BET surface area 315 m2/g, pore volume 0.996 ml/g), activated carbon: Fluka activated carbon (powder, BET surface area 2056 m2/g, pore volume 1.723 ml/g), Si silica: Silica 60, silanized: Merck KGaA (particle size 0.063-0.200 mm, BET surface area 430 m2/g, pore volume 0.535 ml/g). |
Claims (17)
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DE102009029284.5 | 2009-09-08 | ||
PCT/EP2010/061770 WO2011029691A1 (en) | 2009-09-08 | 2010-08-12 | Method for oligomerising olefins |
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US10647628B2 (en) | 2017-02-27 | 2020-05-12 | Evonik Degussa Gmbh | Selective oligomerization of olefins |
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DE202011106025U1 (en) * | 2011-08-14 | 2012-08-17 | BLüCHER GMBH | Activated carbon with metal-based component |
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DE102012202621A1 (en) * | 2012-02-21 | 2013-08-22 | Wacker Chemie Ag | Process for filling a reactor with a catalyst |
KR20130102266A (en) * | 2012-03-07 | 2013-09-17 | 주식회사 씨트리 | Preparation of supported ionic liquid phase |
DE102014200072A1 (en) * | 2014-01-08 | 2015-07-09 | Evonik Industries Ag | Dimerization of olefins |
DE102014209536A1 (en) * | 2014-05-20 | 2015-11-26 | Evonik Degussa Gmbh | Production of high-quality oxo alcohols from unstable raw material sources |
CN109012727B (en) * | 2018-08-08 | 2021-03-23 | 南京晓庄学院 | Half-metallic C4N3Nano plate and preparation method and application thereof |
FR3086551A1 (en) * | 2018-09-28 | 2020-04-03 | IFP Energies Nouvelles | CATALYTIC COMPOSITION BASED ON NICKEL (II) |
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US9682898B2 (en) | 2013-06-27 | 2017-06-20 | Evonik Degussa Gmbh | Oligomerization of C4 streams with very low 1 butene content |
US10370311B2 (en) | 2015-05-28 | 2019-08-06 | Evonik Degussa Gmbh | Hydrogen-assisted adsorption of sulphur compounds from olefin mixtures |
US10647628B2 (en) | 2017-02-27 | 2020-05-12 | Evonik Degussa Gmbh | Selective oligomerization of olefins |
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